DE60313899T2 - IMPROVED DETERGENT - Google Patents

Description

technical area

The Invention relates to synergistic detergent compositions, containing surfactants and swellable polymers for cleaning from hard surfaces are suitable.

technical background

commercial Cleaning compositions for hard surfaces typically comprise one or more surfactants and a variety of abrasive particles dispersed therein. Combinations of surfactants, along with electrolytes, are often used to make a suspending System for to form the abrasive materials as well known in the art is. Various forms of cleaning compositions are available which in the form of liquids, Pastes, gels, powders and bars are present. Typical, in these Compositions used abrasive substances include calcite and dolomites.

Hardness surfaces within the household are kitchen appliances, kitchen walls and floors, countertops and washbasins, bathroom walls, Floors and Installation parts, other floors, etc.; and you encounter different types of dirt on them Surfaces. The dirt that is generally encountered on kitchen appliances and cooking surfaces, is of two kinds; namely the mobile or greasy dirt and the tough or difficult to remove Dirt from dried or sticking food consists. The problem of removing this dirt becomes more pronounced when the tough one Dirt over accumulates a period of time and quite a bit of effort is put into cleaning got to.

in the Generally, the proportion of surfactant in the cleaning compositions up to about 20% and the rest make up other ingredients. abrasive Fabrics, builders and fillers form an important part of the formulation. It is necessary, to add these ingredients to the dispersibility of the surfactant on the surface to be cleaned, especially in hand washing situations, to improve.

Polymers have been used in cleaning compositions for various benefits, such as structuring and soil release functions. EP 883,670 (Unilever, 1998) discloses machine washing dishwashing compositions which have high viscosity. They have a dual chamber structuring system comprising 0.2-2% of a crosslinked polycarboxylate and an azole.

EP-A-1 074 608 discloses laundry detergent tablets of compressed, particulate material. The tablet or a portion thereof contains at least one surfactant Agent, a builder, a water-insoluble but water-swellable, disintegrating agent. More preferably contains the tablet or range thereof at least 5% by weight of the solid surfactant, of which at least a part of a solid nonionic, surface-active Means and not more than 3% by weight of liquid, nonionic surfactant Contains funds.

WHERE 00/42143 discloses detergent compositions for cleaning of laundry or hard surfaces suitable, comprising up to 50 percent by weight of the total Detergent composition of wash active and ghatti gum Gum from the water-swellable, branched hydrocolloids, which are obtained from the species belonging to the genus Anogeissus belong.

WHERE 01/21756 discloses tablets of compacted particulate cleaning composition containing at least one cleaning ingredient selected from the group consisting of organic surfactants, water softening Means and bleaching agents, in which the water-swellable, in water insoluble, promoting decay Material at a higher concentration in at least one zone adjacent to a tablet surface, as in an inner zone, the farther from each surface of the Tablet is.

The Add a big one Quantity of water, along with abrasive substances, builders and fillers, increases the bulk of the product and increases hence the cost and difficulty of transport from the place of manufacture to the place of application.

Thus, there is a need for a concentrated cleaning composition characterized by the Ver can be converted to a ready-to-use product by adding water. This concentrated composition would be a cost savings of shipping and packaging as compared to a dilute composition.

Brief description of the invention

The The present invention provides a synergistic concentrated cleaning composition ready, comprising one or more surfactants and one or more water-swellable polymers that exceed their weight in water can absorb. The composition can become a bulky paste or thick liquid converted by simple addition of water before use become the distribution ability the composition on a large number of to be cleaned surfaces to ensure.

Description of the invention in detail

All mentioned herein Parts and percentages are by weight of the composition unless otherwise stated.

The The present invention thus provides a synergistic cleaning composition prepared comprising surfactants and polymer, wherein: one or more surfactants in an amount of 5-95% wherein nonionic surfactant is at least 40 weight percent the total surfactant is; and one or more swellable in water Polymers that absorb more than their weight in water, in one Amount of 5-95% available; wherein the weight ratio of the surfactant to the water swellable polymer in the range of 1: 0.4 to 0.4: 1 and wherein the water-swellable polymer is selected from the group consisting of consisting of polyacrylic acids, polyacrylates, crosslinked acrylate polymers, guar gum and its derivatives, starch-acrylic grafted Copolymers, hydrolysates of starch-acrylonitrile grafted Copolymers, cross-linked polyoxyethylene, cross-linked carboxymethylcellulose, partially crosslinked, water-swellable polymers such as polyethylene oxide and polyacrylamide, and isobutylene / maleic acid copolymer.

In In the context of the present invention, the term "cleaning composition" refers to compositions in the form of solid powders, tablets, pellets or noodles, or on pastes or gels, in a product with increased volume can be converted by the addition of water. The product thus obtained Can be applied more easily or over distributed the surface to be cleaned become.

surfactants

The Composition according to the invention will comprise one or more surfactants, which are generally anionic, nonionic, cationic or amphoteric surfactants are selected. It is preferred that the surfactant in the composition is 5 to 50%, more preferably 5 to 25% by weight of the composition.

A Suitable class of anionic surfactants are water-soluble salts of organic sulfuric acid monoesters and sulfonic acids having in the molecular structure of a branched or straight-chain Alkyl group, 8-22 Contains C atoms, or an alkylaryl group, the 6-20 Contains C atoms in the alkyl moiety.

• – langkettigen (d.h. 8–22 C-Atom) Alkoholsulfaten (hierin anschließend als PAS bezeichnet), insbesondere jene, erhalten durch Sulfatieren der Fettalkohole, die aus Talg- oder Kokosnussöl hergestellt wurden, oder den synthetischen Alkoholen, die von Erdöl abgeleitet sind;
• – Alkylbenzolsulfonaten, wie jenen, worin die Alkylgruppe 6 bis 20 Kohlenstoffatome enthält;
• – sekundären Alkansulfonaten.

Examples of such anionic surfactants are water-soluble salts of:

• Long-chain (ie 8-22 C-atom) alcohol sulfates (hereinafter referred to as PAS), especially those obtained by sulfating the fatty alcohols prepared from tallow or coconut oil or the synthetic alcohols derived from petroleum;
• Alkylbenzenesulfonates, such as those in which the alkyl group contains from 6 to 20 carbon atoms;
• - secondary alkanesulfonates.

• – Alkylglycerylethersulfaten, insbesondere die Ether von Fettalkoholen, abgeleitet von Talg- und Kokosnussöl;
• – Fettsäuremonoglyceridsulfaten;
• – Sulfaten von ethoxylierten aliphatischen Alkoholen, die 1–12 Ethylenoxygruppen enthalten;
• – Alkylphenolethylenoxyethersulfaten mit 1 bis 8 Ethylenoxyeinheiten pro Molekül und worin die Alkylgruppen 4 bis 14 Kohlenstoffatome enthalten;
• – Das Reaktionsprodukt von Fettsäuren, verestert mit Isethionsäure und neutralisiert mit Alkali.

Also suitable are the salts of:

• - Alkylglycerylethersulfaten, in particular the ethers of fatty alcohols, derived from tallow and coconut oil;
• Fatty acid monoglyceride sulfates;
• Sulfates of ethoxylated aliphatic alcohols containing 1-12 ethyleneoxy groups;
• - Alkylphenolethylenoxyethersulfaten with 1 to 8 ethyleneoxy units per molecule and wherein the Alkylgrup pen contains 4 to 14 carbon atoms;
• The reaction product of fatty acids, esterified with isethionic acid and neutralized with alkali.

• – Die Kondensationsprodukte von aliphatischen Alkoholen mit 8 bis 22 Kohlenstoffatomen, in entweder gerader oder verzweigtkettiger Konfiguration mit Ethylenoxid, wie ein Kokosnussalkohol/Ethylenoxid-Kondensat mit 2 bis 15 Mol Ethylenoxid pro Mol Kokosnussalkohol;
• – Kondensate von Alkylphenolen mit C6-C15-Alkylgruppen mit 5 bis 25 Mol Ethylenoxid pro Mol Alkylphenol;
• – Kondensate von dem Reaktionsprodukt von Ethylendiamin und Propylenoxid mit Ethylenoxid; die Kondensate enthalten 40 bis 80 Gewichtsprozent Ethylenoxygruppen, und mit einem Molekulargewicht von 5 000 bis 11 000.

A suitable class of nonionic surfactants can be broadly described as compounds prepared by the condensation of simple alkylene oxides which are hydrophilic in nature with an aliphatic or alkyl aromatic hydrophobic compound having a reactive hydrogen atom. The length of the hydrophilic or polyoxyalkylene chain bonded to each individual hydrophobic group can be readily adjusted to give a compound having the desired balance between hydrophilic and hydrophobic elements. This allows the selection of nonionic surfactants with the right HLB value. Particular examples include:

• The condensation products of aliphatic alcohols having 8 to 22 carbon atoms, in either a straight or branched chain configuration with ethylene oxide, such as a coconut alcohol / ethylene oxide condensate with 2 to 15 moles of ethylene oxide per mole of coconut alcohol;
• Condensates of alkylphenols having C 6 -C 15 -alkyl groups with from 5 to 25 mol of ethylene oxide per mole of alkylphenol;
• Condensates of the reaction product of ethylene diamine and propylene oxide with ethylene oxide; the condensates contain from 40 to 80 percent by weight of ethyleneoxy groups, and having a molecular weight of from 5,000 to 11,000.

• – Alkylpolyglycoside, die Kondensationsprodukte von langkettigen aliphatischen Alkoholen und Sacchariden darstellen;
• – tertiäre Aminoxide der Struktur RRRNO, worin ein R eine Alkylgruppe mit 8 bis 20 Kohlenstoffatomen darstellt und die anderen R jeweils Alkyl- oder Hydroxyalkylgruppen mit 1 bis 3 Kohlenstoffatomen darstellen, z.B. Dimethyldodecylaminoxid;
• – tertiäre Phosphinoxide der Struktur RRRPO, worin ein R eine Alkylgruppe mit 8 bis 20 Kohlenstoffatomen darstellt und die anderen R jeweils Alkyl- oder Hydroxyalkylgruppen mit 1 bis 3 Kohlenstoffatomen darstellen, z.B. Dimethyldodecylphosphinoxid;
• – Dialkylsulfoxide der Struktur RRSO, worin ein R eine Alkylgruppe mit 10 bis 18 Kohlenstoffatomen darstellt und das andere Methyl oder Ethyl darstellt, z.B. Methyltetradecylsulfoxid;
• – Fettsäurealkylolamide, wie die Ethanolamide;
• – Alkylenoxidkondensate von Fettsäurealkylolamiden;
• – Alkylmercaptane.

Other classes of nonionic surfactants are:

• Alkylpolyglycosides which are condensation products of long-chain aliphatic alcohols and saccharides;
• Tertiary amine oxides of structure RRRNO, wherein one R represents an alkyl group of 8 to 20 carbon atoms and the other R each represents alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for example dimethyldodecylamine oxide;
• Tertiary phosphine oxides of the structure RRRPO, wherein one R represents an alkyl group of 8 to 20 carbon atoms and the other R each represents alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for example dimethyldodecylphosphine oxide;
• Dialkyl sulfoxides of the structure RRSO, wherein one R is an alkyl group of 10 to 18 carbon atoms and the other is methyl or ethyl, for example methyltetradecylsulfoxide;
• Fatty acid alkylolamides, such as the ethanolamides;
• - alkylene oxide condensates of fatty acid alkylolamides;
• - alkylmercaptans.

A special group of surfactants are the tertiary amines by condensation of ethylene and / or propylene oxide with long-chain aliphatic Amines are obtained.

The Compounds behave like nonionic surfactants in alkaline Medium and as cationic surfactants in acidic medium.

It is possibly possible amphoteric, cationic or zwitterionic surfactants in the compositions of the invention include.

suitable amphoteric surfactant compounds which may be used can, are derivatives of aliphatic secondary and tertiary amines, which is an alkyl group having 8 to 18 carbon atoms and an aliphatic Radical substituted with an anionic, water-solubilizing Group containing, for example, sodium 3-dodecylaminopropionate, Sodium 3-dodecylaminopropanesulfonate and sodium N-2-hydroxydodecyl-N-methyltaurate.

Examples for suitable cationic surfactants are found among quaternary ammonium salts with one or more two alkyl or Aralkyl groups having 8 to 20 carbon atoms and two or three small aliphatic (e.g., methyl) groups, e.g. Cetyltrimethylammonium bromide.

Examples for suitable Zwitterionic surfactants are found among derivatives of aliphatic quaternary Ammonium, sulfonium and phosphonium compounds, with an aliphatic Group of 8 to 18 carbon atoms and an aliphatic group, substituted with an anionic, water-solubilizing Group, for example: 3- (N, N-dimethyl-N-hexadecylammonium) propane-1-sulfonate betaine, 3- (Dodecylmethylsulfonium) propane-1-sulfonate betaine and 3- (cetylmethylphosphonium) ethanesulfonate betaine. Other well-known betaines are the alkylamidopropyl betaines, for example those wherein the alkylamido group is derived from coconut oil fatty acids.

Further examples for suitable surfactants are compounds commonly known as surfactants used in the well-known manuals: "Surface Active Agents Band 1, by Schwartz & Perry, Interscience 1949; "Surface Active Agents Band 2, by Schwartz, Perry and Berch, Interscience 1958; the current issue of "McCutcheon's Emulsifiers and Detergents ", published from Manufacturing Confectioners Company; "Tenside-Taschenbuch", H. Stache, 2nd edition, Carl Hauser Verlag, 1981.

It it is particularly preferred that the surfactant is a mixture of anionic and nonionic surfactants in a ratio of at least 1:10 and more preferably at least 1: 1.

Swellable polymers:

The Water swellable polymers are polyacrylic acids and polyacrylates, crosslinked Acrylate polymers, guar gum and its derivatives, starch acrylic grafted Copolymers, hydrolysates of starch-acrylonitrile-grafted Copolymers, cross-linked polyoxyethylene, cross-linked carboxymethylcellulose, partially crosslinked, water-swellable polymers such as polyethylene oxide and polyacrylamide, isobutylene / maleic acid copolymers, etc. The particular preferred water-swellable polymers are polyacrylic acids and the most preferred are crosslinked polyacrylic acids, in part neutralized with the sodium salts. The inventive, in Water swellable polymers are called solids and liquids available, and the preferred forms are solid forms, such as particles, granules, Pellets, flakes, short needles and the like.

It it is preferred that the water-swellable polymer in the composition 5 to 75%, more preferably 5 to 50% by weight of the composition is.

Optional components

Inorganic particulate matter:

A particulate insoluble, solid phase is an optional component of the compositions of the invention.

Preferably includes the particulate Phase an abrasive that is insoluble in water. In the alternative For example, the abrasive may be soluble to some extent and may produce such excess to water present in the composition, when it is mixed with water before use, that solubility of the abrasive substance in the aqueous Phase exceeded and thus the abrasive is in the swollen mixture in the solid phase.

The Gel or paste-forming capacity of the swellable polymers can be reduced in the presence of certain electrolytes. To the For example, calcium ions reduce the swellability of the crosslinked ones polyacrylic acid, which is a water-swellable polymer. Consequently, must one while of selecting the Beware of abrasive substances and inorganic particulate matter to avoid such materials. If its application absolutely necessary, then have to they are applied in minimal quantities.

suitable abrasive substances can from particulate Zeolites, calcites, dolomites, feldspar, silicas, silicates, other carbonates, aluminas, bicarbonates, borates, sulphates and polymeric materials, such as polyethylene.

preferred abrasive materials for use for All-purpose cleaner compositions have a Moh's hardness of 2-6, though abrasive materials with higher Hardness for special Applications can be applied.

preferred average particle sizes for the abrasive Fabric fall in the range 0.5-400 microns, with values of about 5-200 microns preferred are.

Other optional ingredients

The composition of the invention may contain other ingredients that aid its cleaning performance. For example, the composition may include detergency builders such as nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water-soluble phosphates (such as polyphosphates, mixtures of ortho- and pyrophosphates), zeolites and mixtures thereof. The compositions of the invention may also contain, in addition to the ingredients already mentioned, various other optional ingredients such as solvents, colorants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (especially hypohalites) and preservatives.

inorganic particulate Substances and other optional ingredients may be present in an amount of up to to 90% of the composition.

• a) 5–50% von einem oder mehreren Tensiden, die mindestens 40% des Gesamttensidgewichts als anionisches Tensid aufweisen;
• b) 5–75% von einem oder mehreren in Wasser quellbarem Polymer, das mehr als sein Gewicht an Wasser absorbiert und
• c) gegebenenfalls bis zu 90 Gewichtsprozent von anorganischen teilchenförmigen Stoffen und anderen herkömmlichen Bestandteilen.

Thus, according to a preferred aspect of the present invention there is provided a synergistic cleaning composition comprising:

• a) 5-50% of one or more surfactants having at least 40% of the total surfactant weight as anionic surfactant;
• b) 5-75% of one or more water-swellable polymer which absorbs more than its weight in water and
• c) optionally up to 90% by weight of inorganic particulate matter and other conventional ingredients.

• a) 5–25% von einem oder mehreren Tensiden, die mindestens 40% des Gesamttensidgewichts als nichtionisches Tensid aufweisen;
• b) 5–50 Gewichtsprozent von einem oder mehreren in Wasser quellbarem Polymer, das mehr als sein Gewicht an Wasser absorbiert und 10–90 Gewichtsprozent anorganische teilchenförmige Stoffe und andere herkömmliche Bestandteile.

Thus, according to a more preferred aspect of the present invention there is provided a synergistic cleaning composition comprising:

• a) 5-25% of one or more surfactants having at least 40% of the total surfactant weight as a nonionic surfactant;
• b) 5-50% by weight of one or more water-swellable polymer that absorbs more than its weight in water and 10-90% by weight of inorganic particulates and other conventional ingredients.

The Invention will now be with reference to the following non-limiting Examples explained.

Examples:

i. Effect on the polymer-surfactant interaction in the gelation:

As Compositions reported in Table 1 are blended of the surfactant and the polymer. The products are called get a powdery mass. 50 g of water become each of these Given and for products 1-2 minutes leave. The visual appearance of the products after adding water and the gel volume obtained are also shown in Table 1.

Measurement of gel volume (ml) after addition of excess water

• Beispiel 1, Beispiel 4, Beispiel 5 und Beispiel 6 sind Vergleichsbeispiele.

The paste / thick liquids formed in Examples 1-6 above were transferred to separate, divided 250 ml graduated cylinders and the volume was made up to 250 ml by the addition of water. The contents of the cylinders were stirred for one minute and allowed to settle overnight and observed. The contents of the cylinders separated into two phases (Examples 1, 2, 3 and 6). The gel formed by the swellable polymer settled on the bottom while the water layer was at the top. The volume of the gel layer was measured. The volume of the gels (in the presence of an excess amount of water) shows the gel-forming capacity of the swellable polymer in the presence of the surfactants. It will be seen that the more the gel volume, the less the negative impact of the surfactant on the swellable polymer. Table 1

• Example 1, Example 4, Example 5 and Example 6 are comparative examples.

The The data given in Table 1 shows that the polymer used to form of a gel, and in the presence of nonionic surfactants The polymer forms a good, solid-like gel. This shows that the selection of the surfactant in determining the gel strength and the Volume is important, which in turn improves the consistency of the educated Paste determined.

ii. Effect of texture of the surfactant on the gelation:

anionic Surfactant and nonionic surfactant in various proportions, in compositions described in Table 2, it was investigated to determine the effect on gelation. The product was mixed with water and the condition of the gel was examined. The measurement of gel volume (ml) after addition of excess water was determined by the method described above. The Performance was also under consideration the cleaning efficacy.

Measurement of cleaning efficiency:

• Beispiel 7, Beispiel 9, Beispiel 10, Beispiel 11 und Beispiel 12 sind Vergleichsbeispiele.

1 g of the gel formed by adding 100 g to 7.5 g of powder was taken out as a rinse using an auxiliary, and a soiled plate was cleaned. Various parameters of cleaning and application properties were determined during the cleaning process. Based on an overall benefit, cleaning efficiency was rated on a scale of 1-5, where "1" refers to "bad" and "5" refers to "good" performance. Table 2

• Example 7, Example 9, Example 10, Example 11 and Example 12 are comparative examples.

The shown in Table 2 show that the polymer for obtaining Consistent gel is essential, but poor performance shows with respect cleaning (Example 9). When the surfactant in the absence of the polymer is present alone, no gel is obtained and the Reinigungswirk activity is diminished (Examples 10 and 11) because the polymer has the distribution ability of the Active ingredient supports. The performance of the compositions as in Examples 7, 8, 12 and 13, re Gelation and cleaning efficacy, indicates that the right Combination of the surfactant and the polymer to obtain a composition It is important that both optimal cleaning and good gel strength having.

Claims (15)

A synergistic cleaning composition comprising Surfactants and polymer, wherein: a) one or more surfactants in in an amount of 5-95% wherein nonionic surfactant is at least 40 weight percent the total surfactant is; and b) one or more swellable in water Polymers that absorb more than their weight in water, in one Amount of 5-95% available; wherein the weight ratio of the surfactant to the water swellable polymer in the range of 1: 0.4 to 0.4: 1 and wherein the water-swellable polymer is selected from the group consisting of consisting of polyacrylic acids, polyacrylates, crosslinked acrylate polymers, guar gum and its derivatives, starch acrylic grafted Copolymers, hydrolysates of starch-acrylonitrile-grafted Copolymers, cross-linked polyoxyethylene, cross-linked carboxymethylcellulose, partially crosslinked, water swellable polymers such as polyethylene oxide and Polyacrylamide, and isobutylene / maleic acid copolymer. A composition according to claim 1, wherein the in water swellable polymer of polyacrylic acids or partially neutralized sodium salts of crosslinked polyacrylic acids. A composition according to any one of claims 1 to 2, wherein the water swellable polymer 5 to 75% of the composition is. A composition according to claim 3, wherein the in water swellable polymer is 5 to 50% of the composition. A composition according to any one of claims 1 to 4, wherein the surfactants of anionic and nonionic surfactants selected are. A composition according to claim 5, wherein the weight ratio of the anionic to nonionic surfactants is at least 0.1: 1. A composition according to claim 6, wherein the weight ratio of the anionic to nonionic surfactant is 1: 1. A composition according to any one of claims 1 to 7, wherein the composition is total surfactants in the range of 5 to 50% of the composition. A composition according to claim 8, wherein the composition Surfactants in the range of 5 to 25% of the composition. A composition according to any one of claims 1 to 9, wherein the composition is in the form of solid powders, tablets, Pellets, noodles, pastes or gels. A composition according to any one of claims 1 to 10, wherein the water-swellable polymer is in the form of a solid is present. A composition according to claim 11 wherein said in water swellable polymer in the form of particles, granules, pellets, flakes or short needles. A composition according to any one of claims 1 to 12, wherein the composition additionally up to 90% inorganic particulate Fabrics and other conventional Includes ingredients. A composition according to any one of claims 1 to 13, wherein the composition is 10 to 90% of inorganic particulate phase includes. A composition according to claim 13 or 14, wherein the particulate Phase one in water insoluble or partially soluble abrasive substance is.